An Atomic Insight into the Chemical Origin and Variation of the Dielectric Constant in Liquid Electrolytes

被引:150
作者
Yao, Nan [1 ]
Chen, Xiang [1 ]
Shen, Xin [1 ]
Zhang, Rui [2 ]
Fu, Zhong-Heng [1 ]
Ma, Xia-Xia [1 ]
Zhang, Xue-Qiang [1 ]
Li, Bo-Quan [2 ]
Zhang, Qiang [1 ]
机构
[1] Tsinghua Univ, Dept Chem Engn, Beijing Key Lab Green Chem React Engn & Technol, Beijing 100084, Peoples R China
[2] Beijing Inst Technol, Adv Res Inst Multidisciplinary Sci, Beijing 100081, Peoples R China
基金
中国国家自然科学基金; 中国博士后科学基金;
关键词
dielectric constant; liquid electrolytes; molecular dynamics simulations; solvent mixtures; temperature; DIFFUSION-COEFFICIENTS; METAL BATTERIES; LI; TEMPERATURES; SOLVATION; TRANSPORT; DESIGN; MODELS; ANODES; IONS;
D O I
10.1002/anie.202107657
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The dielectric constant is a crucial physicochemical property of liquids in tuning solute-solvent interactions and solvation microstructures. Herein the dielectric constant variation of liquid electrolytes regarding to temperatures and electrolyte compositions is probed by molecular dynamics simulations. Dielectric constants of solvents reduce as temperatures increase due to accelerated mobility of molecules. For solvent mixtures with different mixing ratios, their dielectric constants either follow a linear superposition rule or satisfy a polynomial function, depending on weak or strong intermolecular interactions. Dielectric constants of electrolytes exhibit a volcano trend with increasing salt concentrations, which can be attributed to dielectric contributions from salts and formation of solvation structures. This work affords an atomic insight into the dielectric constant variation and its chemical origin, which can deepen the fundamental understanding of solution chemistry.
引用
收藏
页码:21473 / 21478
页数:6
相关论文
共 53 条
[41]   Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy [J].
Wang, Jiangyan ;
Huang, William ;
Pei, Allen ;
Li, Yuzhang ;
Shi, Feifei ;
Yu, Xiaoyun ;
Cui, Yi .
NATURE ENERGY, 2019, 4 (08) :664-670
[42]   Influence of Dielectric Constant on Ionic Transport in Polyether-Based Electrolytes [J].
Wheatle, Bill K. ;
Keith, Jordan R. ;
Mogurampelly, Santosh ;
Lynd, Nathaniel A. ;
Ganesan, Venkat .
ACS MACRO LETTERS, 2017, 6 (12) :1362-1367
[43]   Nonaqueous liquid electrolytes for lithium-based rechargeable batteries [J].
Xu, K .
CHEMICAL REVIEWS, 2004, 104 (10) :4303-4417
[44]   Electrolytes and Interphases in Li-Ion Batteries and Beyond [J].
Xu, Kang .
CHEMICAL REVIEWS, 2014, 114 (23) :11503-11618
[45]   Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte [J].
Xue, Weijiang ;
Huang, Mingjun ;
Li, Yutao ;
Zhu, Yun Guang ;
Gao, Rui ;
Xiao, Xianghui ;
Zhang, Wenxu ;
Li, Sipei ;
Xu, Guiyin ;
Yu, Yang ;
Li, Peng ;
Lopez, Jeffrey ;
Yu, Daiwei ;
Dong, Yanhao ;
Fan, Weiwei ;
Shi, Zhe ;
Xiong, Rui ;
Sun, Cheng-Jun ;
Hwang, Inhui ;
Lee, Wah-Keat ;
Shao-Horn, Yang ;
Johnson, Jeremiah A. ;
Li, Ju .
NATURE ENERGY, 2021, 6 (05) :495-505
[46]   Advances and issues in developing salt-concentrated battery electrolytes [J].
Yamada, Yuki ;
Wang, Jianhui ;
Ko, Seongjae ;
Watanabe, Eriko ;
Yamada, Atsuo .
NATURE ENERGY, 2019, 4 (04) :269-280
[47]   Regulating Interfacial Chemistry in Lithium-Ion Batteries by a Weakly Solvating Electrolyte** [J].
Yao, Yu-Xing ;
Chen, Xiang ;
Yan, Chong ;
Zhang, Xue-Qiang ;
Cai, Wen-Long ;
Huang, Jia-Qi ;
Zhang, Qiang .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2021, 60 (08) :4090-4097
[48]   Fluorinated Aromatic Diluent for High-Performance Lithium Metal Batteries [J].
Yoo, Dong-Joo ;
Yang, Sungyun ;
Kim, Ki Jae ;
Choi, Jang Wook .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (35) :14869-14876
[49]   Commercialization of Lithium Battery Technologies for Electric Vehicles [J].
Zeng, Xiaoqiao ;
Li, Matthew ;
Abd El-Hady, Deia ;
Alshitari, Wael ;
Al-Bogami, Abdullah S. ;
Lu, Jun ;
Amine, Khalil .
ADVANCED ENERGY MATERIALS, 2019, 9 (27)
[50]   Lithium Metal Anodes with Nonaqueous Electrolytes [J].
Zhang, Ji-Guang ;
Xu, Wu ;
Xiao, Jie ;
Cao, Xia ;
Liu, Jun .
CHEMICAL REVIEWS, 2020, 120 (24) :13312-13348